US 8,765,984 B2 · Assignee: Chevron Phillips Chemical Company LP · Inventors: Upshaw; Thomas A.
Claude can sketch it from the patent text.
The application discloses thiol ester molecules and .alpha.-hydroxy thiol ester molecules having a thiol group located on one of the final two carbon atoms in a carbon chain or a terminal or .alpha.-hydroxyl groups, respectively. The disclosed thiol ester molecules and or .alpha.-hydroxyl thiol ester molecules es may be made from unsaturated ester molecules having one or more terminal alkene groups. The disclosed techniques also provide methods for making unsaturated ester molecules having one or more terminal alkene groups by the metathesis of unsaturated esters having one or more internal carbon-carbon double bonds (e.g. natural source oils). The thiol ester molecules or .alpha.-hydroxy thiol ester molecule may be used in reactions with isocyanate monomers, epoxide monomer, or material having multiple alkene groups to make sealants, coatings, adhesives, and other products.
This section is intended to introduce the reader to aspects of art that may be related to aspects of the present techniques, which are described herein. This discussion is believed to be helpful in providing the reader with background information to facilitate a better understanding of the various aspects of the present techniques. Accordingly, it should be understood that these statements are to be read in this light, and not as admissions of prior art. As chemical and petrochemical technologies have advanced, the products of these technologies have become increasingly prevalent in society. In particular, as techniques for bonding simple molecular building blocks into longer chains, termed polymers, have advanced, the polymer products, typically in the form of various plastics, have been increasingly incorporated into various everyday items. For example, polyurethane polymers and copoly
Ask Claude for concept sketches based only on the patent's text. They are not part of the patent.
What the patent claimed, word for word. All of it is now free to use.
This section is intended to introduce the reader to aspects of art that may be related to aspects of the present techniques, which are described herein. This discussion is believed to be helpful in providing the reader with background information to facilitate a better understanding of the various aspects of the present techniques. Accordingly, it should be understood that these statements are to be read in this light, and not as admissions of prior art.
As chemical and petrochemical technologies have advanced, the products of these technologies have become increasingly prevalent in society. In particular, as techniques for bonding simple molecular building blocks into longer chains, termed polymers, have advanced, the polymer products, typically in the form of various plastics, have been increasingly incorporated into various everyday items. For example, polyurethane polymers and copolymers, made from the reactions of compounds containing hydroxyl groups with compounds containing isocyanate groups, may be used in retail and pharmaceutical packaging, furniture, household items, automobile components, adhesives, coatings, and various other consumer and industrial products.
The chemical industry strives to make these products with low-cost feedstocks that are in abundant supply. Currently, the main feedstocks for polyurethanes, and other plastics, are petrochemicals isolated from petroleum. However, as fossil fuels deplete over time, alternative sources are being sought as replacements for feedstocks. Further, the chemical industry continuously strives to produce products and use feedstocks that are environmentally friendly.
Disclosed herein are thiol ester composition comprising thiol ester molecules having ester linkages comprising a) a residue of a polyol and a carboxylic acid residues having i) at least 4 carbon atoms and ii) a thiol group located on a terminal carbon atom or a carbon atom adjacent to the terminal carbon atom. In an embodiment, the polyol of the residue of polyol was a diol, triol, or a tetraol. In some embodiments, the polyol of the residue of polyol was cyclohexane diol, trimethylol propane, glycerol, pentaerythritol, or combinations thereof. In other embodiments, the polyol of the residue of polyol was glycerol. In an embodiment, the carboxylic acid residues having a thiol group located on a terminal carbon atom or a carbon atom adjacent to the terminal carbon atom have from 10 to 11 carbon atoms. In some embodiments, the carboxylic acid residues having the thiol group located on the terminal carbon atom or the carbon atom adjacent to the terminal carbon atom have only 10 carbon atoms. In other embodiments, the carboxylic acid residues are substantially devoid of hydroxyl groups. In an embodiment, the thiol ester molecules have an average thiol sulfur content of 9 to 16 weight %. In an embodiment, the thiol ester molecules of the thiol ester composition has an average ratio of thiol groups located on a terminal carbon atom to thiol groups located on the carbon atom adjacent to the terminal carbon atom is greater than 5:1. In an embodiment, the average ratio of carboxylic acid residues having a thiol group located on a terminal carbon atom or a carbon atom adjacent to the terminal carbon atom to hydroxyl groups of the polyol of the residue of the polyol is greater than 0.70:1. In a particular embodiment, the thiol ester molecules of the thiol ester composition comprise have ester linkages comprising a) a polyol residue derived from cyclohexane diol, trimethylol propane, glycerol, pentaerythritol, or combinations thereof, and b) carboxylic acid residues having a thiol group located on a terminal carbon atom or a carbon atom adjacent to the terminal carbon atom having from 10 to 11 carbon atoms wherein thiol ester molecules have an average ratio of thiol groups located on a terminal carbon atom to thiol groups located on the carbon atom adjacent to the terminal carbon atom is greater than 5:1, and wherein the thiol ester molecules have an average thiol sulfur content of 9 to 16 weight %.
The thiol ester compositions comprising the thiol ester molecules having thiol groups located on a terminal carbon atom or on a carbon atom adjacent to the terminal carbon atom may be produced by a) contacting ethylene and natural source oil with a metathesis catalyst composition, b) forming unsaturated ester molecules having terminal carbon-carbon double bonds at metathesis conditions capable of forming the unsaturated ester molecules having terminal carbon-carbon double bonds, c) contacting the unsaturated ester molecules having terminal carbon-carbon double bonds and hydrogen sulfide, and d) forming the thiol ester composition comprising thiol ester molecules having the thiol group located on the terminal carbon atom at conditions capable of forming thiol ester molecules having the thiol group located on the terminal carbon. In an embodiment, wherein the metathesis catalyst composition comprises ruthenium carbene metathesis catalyst or a molybdenum carbene metathesis catalyst. In some embodiments, metathesis catalyst comprises dichloro(phenylmethylene) bis(tricyclohexylphosphine) ruthenium or 1,3-bis-(2,4,6-trimethylphenyl)-2-(imidazolidinylidene)(phenylmethylene) dichloro (tricyclohexylphosphine) ruthenium. In an embodiment, the metathesis conditions include a ethylene partial pressure ranging from 50 to 3000 psig and a temperature ranging from 5.degree. C. to 100.degree. C. In an embodiment, the natural source oil comprises a tallow oil, an olive oil, a peanut oil, a castor bean oil, a sunflower oil, a sesame oil, a poppy seed oil, a palm oil, an almond seed oil, a hazelnut oil, a rapeseed oil, a canola oil, a soybean oil, a corn oil, a safflower oil, a cottonseed oil, a camelina oil, a flaxseed oil, or a walnut oil, or any combination thereof. In some embodiments, the natural source oil is soybean oil, corn oil, canola oil, or castor bean oil. In other embodiments, the natural source oil is soybean oil.
Disclosed herein are thiol ester composition comprising thiol ester molecules having ester linkages comprising a) a residue of a polyol and a carboxylic acid residues having i) at least 4 carbon atoms and ii) a terminal .alpha.-hydroxy thiol group. In an embodiment, the polyol of the residue of polyol was a diol, triol, or a tetraol. In some embodiments, the polyol of the residue of polyol was cyclohexane diol, trimethylol propane, glycerol, pentaerythritol, or combinations thereof. In other embodiments, the polyol of the residue of the polyol is derived from glycerol. In an embodiment, the carboxylic acid residues having a terminal .alpha.-hydroxy thiol group have from 10 to 11 carbon atoms. In an embodiment, the carboxylic acid residues having a terminal .alpha.-hydroxy thiol group has only 10 carbon atoms. In an embodiment, the thiol ester molecules have an average thiol sulfur content of 9 to 16 weight %. In an embodiment, the average ratio of carboxylic acid residues having a terminal .alpha.-hydroxy thiol group to hydroxyl groups of the polyol of the residue of the polyol is greater than 0.70:1. In a particular embodiment, the thiol ester molecules of the thiol ester composition have ester linkages comprising a) a polyol residue derived from cyclohexane diol, trimethylol propane, glycerol, pentaerythritol, or combinations thereof, and b) a carboxylic acid residues having a terminal .alpha.-hydroxy thiol group having from 10 to 11 carbon atoms, and wherein the thiol ester molecules have an average thiol sulfur content of 9 to 16 weight %.
The thiol ester compositions comprising the thiol ester molecules having a terminal .alpha.-hydroxy thiol group may be produced by a) contacting ethylene and natural source oil with a metathesis catalyst composition, b) forming unsaturated estermolecules having terminal carbon-carbon double bonds at metathesis conditions capable of forming the unsaturated ester molecules having terminal carbon-carbon double bonds, c) contacting the unsaturated ester moleucles having terminal carbon-carbon double bonds and an oxygen containing compound, d) forming an epoxide ester molecules having terminal epoxide groups at conditions capable of forming epoxide ester molecules having terminal epoxide groups, e) contacting the epoxide ester molecules and hydrogen sulfide, and f) forming the thiol ester composition comprising thiol ester molecules having a terminal .alpha.-hydroxy thiol groups at conditions capable of forming thiol ester molecules. In an embodiment, the metathesis catalyst composition comprises ruthenium carbene metathesis catalyst or a molybdenum carbene metathesis catalyst. In some embodiments, the metathesis catalyst comprises dichloro(phenylmethylene) bis(tricyclohexylphosphine) ruthenium or 1,3-bis-(2,4,6-trimethylphenyl)-2-(imidazolidinylidene)(phenylmethylen- e) dichloro (tricyclohexylphosphine) ruthenium. In an embodiment, the metathesis conditions include a ethylene partial pressure ranging from 50 to 3000 psig and a temperature ranging from 5.degree. C. to 100.degree. C. In an embodiment, the natural source oil comprises a tallow oil, an olive oil, a peanut oil, a castor bean oil, a sunflower oil, a sesame oil, a poppy seed oil, a palm oil, an almond seed oil, a hazelnut oil, a rapeseed oil, a canola oil, a soybean oil, a corn oil, a safflower oil, a cottonseed oil, a camelina oil, a flaxseed oil, or a walnut oil, or any combination thereof. In some embodiments, the natural source oil is soybean oil, corn oil, canola oil, or castor bean oil. In other embodiments, the natural source oil is soybean oil.
To define more clearly the terms used herein, the following definitions are provided. To the extent that any definition or usage provided by any document incorporated herein by reference conflicts with the definition or usage provided herein, the definition or usage provided herein controls.
While compositions and methods are described in terms of "comprising" various components or steps, the compositions and methods can also "consist essentially of" or "consist of" the various components or steps.
The terms "a," "an," and "the" are intended, unless specifically indicated otherwise, to include plural alternatives, e.g., at least one. For instance, the disclosure of "a thiol compound" is meant to encompass one, or mixtures or combinations of more than one, thiol compound, unless otherwise specified.
As used in this disclosure, the term "composition" indicates a system that includes molecules having the indicated features. The molecules may have a variety of structures, which have the indicated described herein. Further, a composition may have a variety of other components present, both intentional and unintentional, which do not have the indicated features and may or may not participate in the reactions described herein.
The term "hydrocarbyl group" is used herein in accordance with the definition specified by IUPAC: a univalent group formed by removing a hydrogen atom from a hydrocarbon (i.e., a group containing only carbon and hydrogen). Similarly, a "hydrocarbylene group" refers to a group formed by removing two hydrogen atoms from a hydrocarbon (either two hydrogen atoms from one carbon atom or one hydrogen atom from two different carbon atoms). A "hydrocarbon group" refers to a generalized group formed by removing one or more hydrogen atoms (as necessary for the particular group) from a hydrocarbon. A "hydrocarbyl group," "hydrocarbylene group," and "hydrocarbon group" can be acyclic or cyclic groups, and/or may be linear or branched. A "hydrocarbyl group," "hydrocarbylene group," and "hydrocarbon group" can include rings, ring systems, aromatic rings, and aromatic ring systems, which contain only carbon and hydrogen. "Hydrocarbyl groups," "hydrocarbylene groups," and "hydrocarbon groups" include, by way of example, aryl, arylene, alkyl, alkylene, cycloalkyl, cycloalkylene, aralkyl, aralkylene, and combinations of these groups, among others. Finally, it should be noted that the "hydrocarbyl group," "hydrocarbylene group," or "hydrocarbon group" definitions include "alkyl group," "alkylene group," and "alkyl groups," respectively, as members.
The term "alkyl group" is used herein in accordance with the definition specified by IUPAC: a univalent group formed by removing a hydrogen atom from an alkane. Similarly, an "alkylene group" refers to a group formed by removing two hydrogen atoms from an alkane (either two hydrogen atoms from one carbon atom or one hydrogen atom from two different carbon atoms). An "alkane group" refers to a generalized group formed by removing one or more hydrogen atoms (as necessary for the particular group) from a alkane. An "alkyl group," "alkylene group," and "alkane group" can be acyclic or cyclic groups, and/or may be linear or branched unless otherwise specified.
The term "organyl group" in used herein in accordance with the definition specified by IUPAC: an organic substituent group, regardless of functional type, having one free valence at a carbon atom. Similarly, an "organylene group" refers to an organic group, regardless of functional type, formed by removing two hydrogen atoms from an organic compound (either two hydrogen atoms from one carbon atom or one hydrogen atom from two different carbon atoms) and an "organic group" refers to a generalized organic group formed by removing one or more hydrogen atoms from an organic compound. Thus, an "organyl group," an "organylene group," and an "organic group" can contain organic functional group(s) and/or atom(s) other than carbon and hydrogen (i.e., an organic group that can comprise functional groups and/or atoms in addition to carbon and hydrogen). For instance, non-limiting examples of atoms other than carbon and hydrogen include halogens, oxygen, nitrogen, phosphorus, and the like. Non-limiting examples of functional groups include ethers, aldehydes, ketones, esters, sulfides, amines, and phosphines, and so forth. An "organyl group," "organylene group," or "organic group" may be aliphatic, inclusive of being cyclic or acyclic, or aromatic. "Organyl groups," "organylene groups," and "organic groups" also encompass heteroatom-containing rings, heteroatom-containing ring systems, heteroaromatic rings, and heteroaromatic ring systems. "Organyl groups," "organylene groups," and "organic groups" may be linear or branched unless otherwise specified. Finally, it should be noted that the "organyl group," "organylene group," or "organic group" definitions include "hydrocarbyl group," "hydrocarbylene group," "hydrocarbon group," respectively, and "alkyl group," "alkylene group," and "alkyl group," respectively, as members.
The term "natural" refers to materials obtained, by any method, from naturally occurring fruits, nuts, vegetables, plants and animals. As an example, "natural source oil" refers to source oils extracted, and optionally purified, from naturally occurring fruits, nuts, vegetables, plants and animals. Additionally, "unsaturated natural source oil" refers to unsaturated source oils extracted, and optionally purified, from naturally occurring fruits, nuts, vegetables, plants, and animals. It should be noted that "natural source oil" and "unsaturated natural source oil" also includes the respective oils extracted, and optionally purified, from genetically modified nuts, vegetables, plant, and animal sources.
The term "natural source raw material" refers to materials obtained by extraction, chemical breakdown, or chemical processing of "natural" materials. A non-limiting example includes natural source oils that can be extracted from naturally occurring fruits, nuts, vegetables, plants and animals. As another non-limiting example, glycerol and carboxylic acids or carboxylic acid esters, saturated or unsaturated, can be produced and isolated by the chemical processing of triglycerides extracted from naturally occurring fruits, nuts, vegetables, plants, and animals.
The term "thiol ester composition" refers to a composition that includes "thiol ester molecules." The thiol ester molecule has at least one thiol group and at least one ester group within the thiol ester molecule.
The term "hydroxy thiol ester composition" refers to a composition that includes "hydroxy thiol ester molecules." The hydroxy thiol ester molecule has at least one thiol group, at least one ester group, and at least one hydroxy or alcohol group within the hydroxy thiol ester molecule. The term ".alpha.-hydroxy thiol ester" refers to a composition that includes ".alpha.-hydroxy thiol ester molecules." The .alpha.-hydroxy thiol ester molecule has at least one thiol group, and one ".alpha.-hydroxy thiol group." The ".alpha.-hydroxy thiol group" has a hydroxy group and a thiol group on adjacent carbon atoms.
The term "unsaturated ester composition" refers to a composition that includes "unsaturated ester molecules." The unsaturated ester molecules have at least one ester group and at least one carbon-carbon double bond within the unsaturated ester molecule.
An ester molecule having an ester linkage comprising a residue of a polyol and a carboxylic acid residue describes esters formed via the combination of the hydroxy group(s) of the polyol and the carboxylic acid group of the carboxylic acid. It should be noted that this description does not mean that the step of forming the particular ester occurs via a reaction between the polyol and carboxylic acid, unless specifically recited as such. The description is only a method for describing the particular ester.
The term "polyol of the residue of the polyol" refers to the parent polyol that formed the residue of the polyol.
For any particular compound disclosed herein, any structure presented also encompasses all conformational isomers, regioisomers, and stereoisomers that may arise from a particular set of substituents, unless otherwise specified. The structure also encompasses all enantiomers, diastereomers, and other optical isomers whether in enantiomeric or racemic forms, as well as mixtures of stereoisomers, as would be recognized by a skilled artisan, unless otherwise specified.
All publications and patents mentioned herein are incorporated herein by reference for the purpose of describing and disclosing the constructs and methodologies described in the publications, which might be used in connection with the presently described invention. The publications discussed throughout the text are provided solely for their disclosure prior to the filing date of the present application. Nothing herein is to be construed as an admission that the inventors are not entitled to antedate such disclosure by virtue of prior invention.
The present techniques generally relate to thiol ester compositions comprising thiol ester molecules having a thiol group located on a terminal carbon atom or a thiol group located on a carbon atom adjacent to a terminal carbon atom. The present techniques, also relate to .alpha.-hydroxy thiol ester compositions comprising, or consisting essentially of, thiol ester molecules having a terminal .alpha.-hydroxy thiol group.
Generally, the techniques for forming thiol ester compositions comprising thiol ester molecules having a thiol group located on a terminal carbon atom or a thiol group located on a carbon atom adjacent to a terminal carbon atom include forming unsaturated ester compositions comprising, or consisting essentially of, unsaturated ester molecules having terminal carbon-carbon double bonds and reacting the unsaturated ester compositions comprising, or consisting essentially of, unsaturated ester molecules having terminal carbon-carbon double bonds to form the thiol ester compositions comprising thiol ester molecules having a thiol group located on a terminal carbon atom or a thiol group located on a carbon atom adjacent to a terminal carbon atom. The techniques for forming the .alpha.-hydroxy thiol ester compositions comprising, or consisting essentially of, thiol ester molecules having a terminal .alpha.-hydroxy thiol group generally include forming unsaturated ester compositions comprising, or consisting essentially of, unsaturated ester molecules having terminal carbon-carbon double bonds and reacting the unsaturated ester compositions comprising, or consisting essentially of, unsaturated ester molecules having terminal carbon-carbon double bonds with an oxygen containing compound to form an epoxide ester composition comprising, or consisting essentially of, epoxide ester molecules having terminal epoxide groups, and subsequently reacting the epoxide ester composition comprising, or consisting essentially of, epoxide ester molecules having terminal epoxide groups, with hydrogen sulfide to form an .alpha.-hydroxy thiol ester compositions comprising, or consisting essentially of, thiol ester molecules having a terminal .alpha.-hydroxy thiol group.
The thiol ester compositions comprising, or consisting essentially of, thiol ester molecules having a thiol group located on a terminal carbon atom or a thiol group located on a carbon atom adjacent to a terminal carbon atom and the .alpha.-hydroxy thiol ester compositions comprising, or consisting essentially of, thiol ester molecules having a terminal .alpha.-hydroxy thiol group may have advantages over previous materials. For example, the close proximity of the thiol groups to a terminal carbon atom may provide advantages in producing thiourethanes, polythiourethanes, epoxy compositions, and materials produced utilizing the thiol-ene reaction.
One or more specific embodiments of the compositions and techniques to produce the compositions are described herein. In an effort to provide a concise description of these embodiments, not all features of an actual implementation are described. It should be appreciated that in the development of any such actual implementation, as in any engineering or design project, numerous implementation-specific decisions must be made to achieve the developer's specific goals, such as compliance with system-related and business-related constraints, which may vary from one implementation to another. Moreover, it should be appreciated that such a development effort might be complex and time consuming, but would nevertheless be a routine undertaking of design, fabrication, and manufacture for those of ordinary skill having the benefit of this disclosure.
Thiol Ester Compositions
In an aspect, the present invention relates to thiol ester compositions comprising, or consisting essentially of, thiol ester molecules having a thiol groups located on terminal carbon atoms and/or thiol groups located on a carbon atom adjacent to a terminal carbon atom. In an aspect, thiol ester molecules may be described as comprising, consisting essentially of, one or more functional groups present in the thiol ester molecules of the thiol ester composition. Each of the functional groups that may be present in the thiol ester molecules are independently described herein and may be utilized in any combination to describe the thiol ester molecules.
The independent functional groups that can be utilized to describe the thiol ester molecules having a thiol groups located on terminal carbon atoms and/or thiol groups located on a carbon atom adjacent to a terminal carbon atom include: the location of the thiol group, the number of (or average number of) ester groups per thiol ester molecule, the number of (or average number of) thiol groups per thiol ester molecule, the ratio of (or average ratio of) thiol groups to ester groups, the number of (or average number of) carbon-carbon double bonds per thiol ester molecule, the average thiol sulfur content of the thiol ester molecules. In some embodiments, the thiol ester molecules have thiol groups located on terminal carbon atoms and/or thiol groups located on a carbon atom adjacent to a terminal carbon atom may be substantially devoid of hydroxyl groups.
The thiol ester molecules of the thiol ester compositions may be produced from any unsaturated ester having terminal double bonds, as described herein. It should be noted that the feedstock unsaturated esters having terminal double bonds may have multiple terminal double bonds and may contain many different unsaturated ester molecules having terminal double bonds. This fact, combined with carbon-carbon double bond reactivity and statistical probability, dictate that each thiol ester molecule having thiol groups located on terminal carbon atoms and/or thiol groups located on a carbon atom adjacent to a terminal carbon atom of the thiol ester molecule may not have the same number of functional groups, the same ratios of functional groups, and/or the same additional features. Thus, the number of functional group, ratios of functional groups, and/or additional features of the thiol ester molecules having thiol groups located on terminal carbon atoms and/or thiol groups located on a carbon atom adjacent to a terminal carbon atom of the thiol ester molecule may be referred to as an average per thiol ester molecule within the thiol ester composition.
In an embodiment, the thiol ester molecules having thiol groups located on terminal carbon atoms and/or thiol groups located on a carbon atom adjacent to a terminal carbon atom have at least 2 ester groups; alternatively at least 3 ester groups; or alternatively, at least 4 ester groups. In other embodiments, the thiol ester molecules having thiol groups located on terminal carbon atoms and/or thiol groups located on a carbon atom adjacent to a terminal carbon atom have from 2 to 8 ester; alternatively, 3 to 6 ester groups; alternatively, 3 to 4 ester groups; alternatively, only 3 ester groups; or alternatively, only 4 ester groups. In further embodiments, the thiol ester molecules having thiol groups located on terminal carbon atoms and/or thiol groups located on a carbon atom adjacent to a terminal carbon atom have an average of at least 2 ester groups per thiol ester molecule; alternatively, an average of at least 2.5 ester groups per thiol ester molecule; or alternatively, an average of at least 3 ester groups per thiol ester molecule. In yet further embodiments, the thiol esters have an average of from 2 to 8 ester groups per thiol ester molecule; alternatively, an average of from 2 to 7 ester groups per thiol ester molecule; alternatively, an average of from 2.5 to 5 ester groups per thiol ester molecule; or alternatively, an average of from 3 to 4 ester groups per thiol ester molecule. In yet other embodiments, the thiol ester molecules having thiol groups located on terminal carbon atoms and/or thiol groups located on a carbon atom adjacent to a terminal carbon atom have an average of about 3 ester groups per thiol ester molecule; or alternatively, an average of about 4 ester groups per thiol ester molecule.
In an embodiment, the thiol ester molecules having thiol groups located on terminal carbon atoms and/or thiol groups located on a carbon atom adjacent to a terminal carbon atom of the thiol ester composition have at least 2 thiol groups; alternatively, at least 3 thiol groups; or alternatively, at least 4 thiol groups. In other embodiments, the thiol ester molecules having thiol groups located on terminal carbon atoms and/or thiol groups located on a carbon atom adjacent to a terminal carbon atom have from 2 to 8 thiol groups; alternatively, 3 to 6 thiol groups; alternatively, 3 to 4 thiol groups; alternatively, only 3 thiol groups; or alternatively, only 4 thiol groups. In further embodiments, the thiol ester molecules having thiol groups located on terminal carbon atoms and/or thiol groups located on a carbon atom adjacent to a terminal carbon atom have an average of at least 1.5 thiol groups per thiol ester molecule; alternatively, an average of at least 2.5 thiol groups per thiol ester molecule; or alternatively, an average of at least 3 thiol groups per thiol ester molecule. In yet further embodiments, the thiol ester molecules have an average of from 1.5 to 8 thiol groups per thiol ester molecule; alternatively, an average of from 2 to 7 thiol groups per thiol ester molecule; alternatively, an average of from 2.5 to 5 thiol groups per thiol ester molecule; or alternatively, an average of from 3 to 4 thiol groups per thiol ester molecule. In yet other embodiments, the thiol ester molecules having thiol groups located on terminal carbon atoms and/or thiol groups located on a carbon atom adjacent to a terminal carbon atom have an average of about 3 thiol groups per thiol ester molecule; or alternatively, an average of about 4 thiol groups per thiol ester molecule.
In an embodiment, the thiol group, of thiol ester molecules, may be located on a terminal thiol atom, located on a carbon adjacent to a terminal carbon atom, or a mixture thereof. In some embodiments, the thiol group of the thiol ester molecule may be located on a terminal carbon atom group; alternatively, the thiol group of the thiol ester molecule may be located on the carbon atom adjacent to a terminal carbon atom.
Generally, the location of the thiol group within the thiol ester molecule may depend upon the particular method utilized to produce it. For example, when reacting unsaturated esters having a terminal carbon-carbon double bond located at a terminal position, it may be possible to choose reaction conditions to produce a thiol ester molecules having a thiol group located on a terminal carbon atom (forming a primary thiol group) or a thiol group located on the carbon atom adjacent to the terminal carbon atom (forming a secondary or tertiary thiol group). It should be noted that in further reactions, primary, secondary, and tertiary thiol groups may have different reactivities. Consequently, it may be desirable to control the ratio of (or average ratio of) thiol groups located on a terminal carbon atom to thiol group located on the carbon atom adjacent to the terminal carbon atom. In some embodiments, the average ratio of thiol groups located on a terminal carbon atom to thiol groups located on the carbon atom adjacent to the terminal carbon atom is greater than 5:1; alternatively, greater than 8:1; or alternatively, greater than 10:1. In other embodiments the average ratio of thiol groups located on a terminal carbon atom to thiol groups located on the carbon atom adjacent to the terminal carbon atom is greater than 1:5; alternatively, greater than 1:8; or alternatively, greater than 1:10.
In an embodiment, the thiol ester molecules may contain carbon-carbon double bonds. These carbon-carbon double bonds may result from incomplete conversion of the feedstock during the reaction with hydrogen sulfide described herein. In some embodiments, the average ratio of carbon-carbon double bonds to thiol groups is less than 1:5; alternatively, less than 1:7; or alternatively, less than 1:10.
In another aspect, the thiol ester molecules within the thiol ester compositions may be described as having ester linkages comprising a residue of a polyol and a carboxylic acid residue having a thiol group. Additional features of the residue of the polyol and carboxylic acid residue having a thiol group are independently described herein and may be utilized in any combination to further describe the thiol ester molecules.
The thiol ester molecules described as having ester linkages comprising a residue of a polyol and a carboxylic acid residue having a thiol group may be produced from any unsaturated ester, as described herein. It should be noted that the feedstock unsaturated esters may have multiple double bonds and may contain many different unsaturated ester molecules. This fact, combined with carbon-carbon double bond reactivity and statistical probability, dictate that each thiol ester molecule having ester linkages comprising a residue of a polyol and a carboxylic acid residue having a thiol group may not have the same structure. Thus, particular features of the thiol ester molecules having ester linkages comprising a residue of a polyol and a carboxylic acid residue having a thiol group may be described as an average per thiol ester molecule.
In an embodiment, the thiol ester molecule having ester linkages comprises a residue of a polyol and a carboxylic acid residues having a thiol group. The residue of the polyol and the carboxylic acid residue having a thiol group are independent elements of thiol ester molecules having ester linkage. Consequently, the features of the residue of the polyol and the carboxylic acid having a thiol group are independently described herein and may be used in any combination to describe the thiol ester molecules having ester linkages may comprise residue of a polyol and at least two carboxylic acid residues having a thiol group.
The carboxylic acid residue having a thiol group may be further described by its structural features. These structural features are independently described herein and may be utilized in any combination to describe the carboxylic acid residue of the thiol ester molecules having ester linkages comprising a residue of a polyol and carboxylic acid residues having a thiol group.
In an embodiment, the carboxylic acid residue having the thiol group is linear. In another embodiment, the carboxylic acid residue having the thiol group is branched.
In an embodiment, the thiol group of the carboxylic acid residue may be located on a terminal carbon atom (a carboxylic acid residue having a thiol group located on a terminal carbon atom), located on a carbon adjacent to a terminal carbon atom (a carboxylic acid residue having a thiol group located on a carbon atom adjacent to a terminal carbon atom), or a mixture thereof. In some embodiments, the thiol group of the carboxylic acid residue may be located on a terminal carbon atom group; alternatively, the thiol group of the carboxylic acid residue may be located on the carbon atom adjacent to a terminal carbon atom. In an embodiment, the average ratio of carboxylic acid residues having thiol groups located on a terminal carbon atom to carboxylic acid residues having thiol groups located on the carbon atom adjacent to the terminal carbon atom is greater than 5:1; alternatively, greater than 8:1; or alternatively, greater than 10:1. In other embodiments the average ratio of carboxylic acid residues having thiol groups located on a terminal carbon atom to carboxylic acid residues having thiol groups located on the carbon atom adjacent to the terminal carbon atom is greater than 1:5; alternatively, greater than 1:8; or alternatively, greater than 1:10.
In an embodiment, the carboxylic acid residue having a thiol group located on a terminal carbon atom and/or thiol group located on a carbon atom adjacent to a terminal carbon atom may have at least 4 carbon atoms; alternatively, at least 6 carbon atoms; or alternatively, at least 8 carbon atoms. In some embodiments, the carboxylic acid residue having a thiol group located on a located on a terminal carbon atom and/or thiol group located on a carbon atom adjacent to a terminal carbon atom may have from 4 to 20 carbon atoms; alternatively, from 6 to 18 carbon atoms; alternatively, from 8 to 14 carbon atoms; alternatively, from 10 to 11 carbon atoms; alternatively, only 10 carbon atoms; or alternatively, only 11 carbon atoms. In an embodiment, the carboxylic acid residue having a thiol group located on a located on a terminal carbon atom and/or thiol group located on a carbon atom adjacent to a terminal carbon atom may have an average of at least 4 carbon atoms; alternatively, at least 6 carbon atoms; or alternatively, at least 8 carbon atoms. In some embodiments, the carboxylic acid residue having a thiol group located on a located on a terminal carbon atom and/or thiol group located on a carbon atom adjacent to a terminal carbon atom may have an average of 4 to 20 carbon atoms; alternatively, of 6 to 18 carbon atoms; alternatively, of 8 to 14 carbon atoms; alternatively, of 10 to 11 carbon atoms; alternatively, of about 10 carbon atoms; or alternatively, of about 11 carbon atoms.
In an embodiment, the carboxylic acid residue having a thiol group is substantially devoid of hydroxyl group. In further embodiments, the carboxylic acid residue having a thiol group is devoid of hydroxyl groups. In yet other embodiments, the carboxylic acid residue having a thiol group is substantially devoid of other functional groups. In further embodiments, the carboxylic acid residue having a thiol group is devoid of other functional groups (i.e. outside of the thiol group located on a terminal carbon atom or the thiol group located on a carbon atom adjacent to a terminal carbon atom and the carbonyl group forming the ester linkage, the carboxylic acid contains only carbon and hydrogen).
In an embodiment, the carboxylic acid residues having a thiol group located on a terminal carbon atom may have Structure CRT 1
##STR00001## wherein p may be positive integer ranging from 1 to 17; alternatively from 3 to 15; alternatively, from 5 to 11; or alternatively 7 to 8. In some embodiments, p may be 7 or alternatively 8. In other embodiments, p may represent an average number (whole or fractional) of carbon atom ranging from 1 to 17; alternatively from 3 to 15; alternatively, from 5 to 11; alternatively 7 to 8; alternatively about 7; or alternatively, about 8. Within the carboxylic acid residue structure CRT 1 the dashed line is the bond to the oxygen atom of the ester linkage.
In an embodiment, the carboxylic acid residues having a thiol group located on a carbon atom adjacent to a terminal carbon atom may have Structure CRT 2
##STR00002## wherein p may be positive integer ranging from 1 to 17; alternatively from 3 to 15; alternatively, from 5 to 11; or alternatively 7 to 8. In some embodiments, p may be 7 or alternatively 8. In other embodiments, p may represent an average number (whole or fractional) of carbon atom ranging from 1 to 17; alternatively from 3 to 15; alternatively, from 5 to 11; alternatively 7 to 8; alternatively about 7; or alternatively, about 8. Within the carboxylic acid residue structure CRT 2 the dashed line is the bond to the oxygen atom of the ester linkage.
The description continues in the full USPTO document.
About 5,912 words. The USPTO PDF has it with every drawing.
Fees are due 3.5, 7.5 and 11.5 years after grant. This patent expired on July 1, 2026, so the fee marked "not paid" was the one that went unpaid.
Methods and Systems for Making Thiol Compounds from Terminal Olefinic Compounds
Filed Apr 2009 · published Oct 2009Methods and Systems for Making Thiol Compounds from Terminal Olefinic Compounds
Filed May 2012 · published Sep 2012Methods and systems for making thiol compounds from terminal olefinic compounds
Filed May 2012 · granted Jul 2014Earlier publications, parents and continuations. None of them can still be enforced, or this patent would not be listed.
Prior art cited by the examiner or applicant. Useful when you check your own idea for novelty.
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